JP2843855B2 - Cyanine compounds - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel cyanine compound.

2. Related Art and Problems Thereof Conventionally, most inorganic recording media for semiconductor lasers have a recording layer mainly composed of tellurium. However, tellurium-based materials have problems such as being toxic, poor in corrosion resistance, expensive, and incapable of achieving high density. Development of organic dyes to replace such tellurium-based inorganic materials Is taking place.

Important characteristics required of the organic dye as a recording medium are as follows.

(1) A material that strongly absorbs near-infrared light in the vicinity of 700 to 900 nm and is accompanied by shape changes such as melting, sublimation, and decomposition due to its thermal energy.

(2) It is desirable that the dye film reflects light strongly for signal detection during reproduction.

(3) Since the recording layer is formed by a wet coating method, it has good solubility in a solvent.

(4) It should be excellent in shape stability and preservability after recording, not deteriorated by reproduction light, and practically endurable for more than 10 years.

Organic dyes are less toxic than the above inorganic materials,
Although it has the advantages of being excellent in corrosion resistance, inexpensive, and capable of achieving high density, among the above characteristics (1) to (4),
In particular, an organic dye satisfying the above characteristics (2) and (3) has not been found yet.

Means for Solving the Problems One object of the present invention is to provide a cyanine compound which can be suitably used as an organic near-infrared absorbing dye of an optical disk recording medium for a semiconductor laser.

Another object of the present invention is to provide a cyanine compound having the above-mentioned characteristics (1) to (4) required as an organic near-infrared absorbing dye for an optical disk recording medium for a semiconductor laser.

Another object of the present invention is to provide a cyanine-based compound having a high reflectivity comparable to that of tellurium-based inorganic materials.

Another object of the present invention is to provide a cyanine-based compound having extremely good solvent solubility.

The cyanine compound of the present invention is a novel compound not described in any literature, and is represented by the following general formula (1).

[In the formula, R ¹ represents a hydrogen atom or a lower alkyl group. R ² represents a lower alkyl group which may have a substituent. X and Y are the same or different and each represents a methylene group or an oxygen atom. Z represents an acidic residue. n represents 2 or 3. In the general formula (1), each group represented by R ¹ , R ² and Z is specifically as follows.

Examples of the lower alkyl group include methyl, ethyl, n
-Propyl, isopropyl, n-butyl, isobutyl,
Examples thereof include C _1-8 alkyl groups such as tert-butyl, n-hexyl, n-heptyl and n-octyl groups.

As the substituent substituted on the lower alkyl group,
For example, a C _1-8 alkoxy group, hydroxyl group, sulfonic acid group, carboxy group, (C _1-8 alkyl) amino group, phenylsulfonylamino group, p-methylphenylsulfonylamino group, acetoxy group, (C _{1 -3} alkoxy) carbonyl group, (C _1-3 alkoxy) (C _1-3 alkoxy) carbonyl group and the like. Specific examples of the lower alkyl group having such a substituent include methoxymethyl, ethoxyethyl, 2-methoxyethyl, 2-ethoxyethyl, 2- (n-butoxy) ethyl, n-butoxyethyl, 2-hydroxyethyl, _{(CH 2) m -SO 3 Na} ( where m is an integer from 1 to 8), methylaminomethyl, dimethylaminomethyl, 2- (p-methyl phenylalanine sulfonylamino) ethyl, acetoxymethyl, 2-acetoxyethyl, Examples include methoxycarbonylmethyl, methoxymethoxymethyl, and 2-ethoxyethoxyethyl groups.

 Z represents a halogen atom, an alkyl sulfate residue,
Reel sulfonate residue, perchlorate residue, tetra
Examples include fluoroborate residues and arylcarboxylic acid residues
Can be shown. When Z is a halogen atom, Z Examples of
As Cl , Br , I , F Etc. can be exemplified. Z is
When it is an alkyl sulfate residue, Z As a specific example of
CH_ThreeSO_Four , C_TwoH_FiveSO_Four , N-C_ThreeH₇SO_Four , N-C_FourH₉SO_Four
Etc. can be exemplified. Z is an arylsulfonate residue
Then Z As a specific example of Can be exemplified. When Z is a perchlorate residue, Z
Specific examples of ClO_Four Etc. can be exemplified. Z is tetra
When it is a fluoroborate residue, Z As a specific example of
Is BF_Four Etc. can be exemplified. Z is an arylcarboxylic acid
If it is a residue, Z As a specific example ofCan be exemplified.

The compound of the present invention represented by the above general formula (1) can be produced by various methods, and if it shows a preferable method, it can be easily produced, for example, by the following method.

That is, the compound of the present invention Wherein R ¹ , R ² , X, Y and Z are the same as above. ] To the indolenium salt represented by the general formula Wherein n is the same as above. ] Is produced by subjecting a compound represented by the formula to a condensation reaction.

The above condensation reaction is carried out in the presence of a fatty acid salt in a dehydrated organic acid. Examples of the fatty acid salt include sodium acetate, potassium acetate, calcium acetate, sodium propionate, potassium propionate and the like, which are usually added in an amount of 0.5 to 1 mol of the compound of the formula (2).
About 3 moles, preferably about 1 to 2 moles.
Examples of the dehydrating organic acid include acetic anhydride, propionic anhydride, butyric anhydride, and γ-butyrolactone. Such a dehydrating organic acid is generally used in an amount of about 10 to 100 mol, preferably about 20 to 50 mol, per 1 mol of the compound of the general formula (2). Compound of general formula (2) and general formula (3)
The use ratio of the compound is usually 0.2
It is good to be about 1.5-fold mole, preferably about 0.4-0.7 mole. The above reaction suitably proceeds usually at about 50 to 150 ° C, preferably 70 to 140 ° C, and is generally completed in about 10 to 60 minutes.

Indolenium salt of the above general formula (2) (general formula (2a)
And the compound of the general formula (2b)) are novel compounds not described in the literature, and the salts are produced, for example, according to the following method.

[In the formula, Z ₁ represents an acidic residue other than a perchlorate residue and a tetrafluoroborate residue, and Z ₂ represents a perchlorate residue or a tetrafluoroborate residue. R ¹ , R ² , X and Y
Is the same as above. A known aniline derivative represented by the general formula (4) and a known 3-bromo-3-methyl-2 represented by the formula (5)
The reaction with butanone is carried out in the presence of a deoxidizing agent.
Examples of the deoxidizing agent include pyridine, triethylamine,
Tertiary amines such as tri-n-propylamine and tri-n-butylamine; alkali metal carbonates such as sodium carbonate, potassium carbonate and calcium carbonate; sodium acetate;
Examples thereof include alkali metal acetates such as potassium acetate and calcium acetate. These are generally used in an amount of about 0.3 to 5 moles, preferably about 0.5 to 1.5 moles, per mole of the compound of the formula (4). The ratio of the compound (4) to the compound (5) is usually about 0.3 to 5 times, preferably about 0.5 to 1.5 times, the molar amount of the former. The reaction is usually performed at room temperature to about 200 ° C., preferably 50 to 1
The reaction is carried out at about 50 ° C., and is generally completed in about several hours to 25 hours, preferably about 5 to 15 hours.

The compound represented by the general formula (2a) is produced by reacting an indolenine derivative represented by the general formula (6) with an alkylating agent. Examples of the alkylating agent include alkyl toluene sulfonates such as methyl toluene sulfonate, ethyl toluene sulfonate, n-propyl toluene sulfonate, isopropyl toluene sulfonate, and n-butyl toluene sulfonate; ethyl bromide;
-Alkyls such as propyl, n-butyl bromide, ethyl iodide, n-propyl iodide, n-propyl chloride, n-butyl chloride, dialkyl sulfates such as dimethyl sulfate, diethyl sulfate, etc. Mixtures (for example, mixtures of inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid and propionic acid with ethylene oxide and propylene oxide), and alkyl sultone such as methyl sultone, ethyl sultone, propyl sultone and butyl sultone. Can be The amount of the alkylating agent to be used per 1 mol of compound (6) is usually about 0.3 to 5 times, preferably 0.5 to 2 times.
The amount is preferably about twice the molar amount. The reaction is carried out without solvent or with toluene, alkylbenzene such as xylene, n-octane, n-decane, cyclohexane, aliphatic hydrocarbons such as decalin, benzene, naphthalene, aromatic hydrocarbons such as tetralin, trichloroethane, The reaction is carried out in a solvent such as halogenated hydrocarbons such as tetrachloroethane, chlorobenzene and dichlorobenzene. The reaction is usually carried out at room temperature to about 200 ° C., preferably about 50 to 150 ° C., and is completed in about 2 to 30 hours, preferably about 5 to 25 hours.

The compound represented by the general formula (7) is produced by treating the compound (2a) with an alkali in a suitable solvent, for example, water. Any conventionally used alkali can be used as the alkali to be used, and examples thereof include sodium hydroxide and potassium hydroxide. The amount of the alkali to be used is generally about 1 to 20 moles, preferably about 1 to 5 moles per 1 mole of compound (2a). The amount of the solvent to be used is generally about 2 to 100-fold molar amount, preferably about 2 to 20-fold molar amount, per 1 mol of compound (2a). The above reaction is usually performed at 0 to 150 ° C.
C., preferably about 0 to 100.degree. C., and is generally completed in about several tens of minutes to about 10 hours, preferably about 1 to 5 hours.

The compound represented by the general formula (2b) is obtained by converting the compound represented by the general formula (8) into the compound (7), such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, isobutyl alcohol, tert-butyl alcohol and the like. In benzene, toluene, xylene, n-octane, n-decane, cyclohexane, decalin, tolcloethane, tetrachloroethane, chlorobenzene, dichlorobenzene and other suitable solvents. It is manufactured by
The compound (7) and the compound (8) are usually used in an amount of about 0.3 to 10 times, preferably about 0.5 to 3 times, the molar amount of the former compound. The reaction is 0
The reaction is performed at about 70 ° C., and is generally completed in about 10 minutes to 3 hours.

The compound of the present invention thus obtained is easily isolated and purified from the reaction mixture by a conventional isolation and purification means, for example, recrystallization, column separation and the like.

Effects of the Invention The compounds of the present invention represented by the above general formula (1) include alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, isobutanol and tert-butanol, and fatty acids such as dichloromethane and dichloroethane. It shows good solubility in organic solvents such as halogenated hydrocarbons, has a maximum absorption wavelength at 670 to 830 nm, and has a high molar extinction coefficient. Further, when used as an optical disk recording medium for a semiconductor laser, the light reflectance by the reproduced laser light is extremely high, and is particularly useful. Further, the compound of the present invention can be suitably used as a dye for a filter, or a photoreceptor for copying and printing, or a sensitizing dye for a photoreceptor, because the compound has sharper absorption than a general dye. Further, the compound of the present invention is also useful as a pharmaceutical diagnostic agent such as a liver function test agent, a dye for LB film and the like.

Examples The production examples of the compound (2) are shown below as reference examples, and then the production examples of the compound of the present invention are shown.

Reference Example A mixture of 20.57 g of 3,4-methylenedioxyaniline, 24.76 g of 3-bromo-3-methyl-2-butanone and 75 ml of pyridine was reacted at 50 to 55 ° C. for 5 hours, and further reacted at reflux for 10 hours. . After completion of the reaction, the mixture was poured into 100 ml of water, extracted with 50 ml of dichloromethane, and after removing the solvent, vacuum distillation was performed to remove 2,2.
3,3-trimethyl-5,6-methylenedioxyindolenine
11.64 g was obtained.

Boiling point 134-136 ° C./4-5 mmHg 2.16 g of 2,3,3-trimethyl-5,6-methylenedioxyindolenin obtained above, p-toluenesulfonic acid n
A mixture of 13.67 g of -butyl and 40 ml of chlorobenzene was reacted under reflux for 20 hours. After completion of the reaction, 1- (n
-Butyl) -2,3,3-trimethyl-5,6-methylenedioxyindolenium toluenesulfonate.

20 g of 20% NaOH was added to this extract, reacted at 70 ° C. for 3 hours, and extracted with 30 ml of toluene. After the toluene was distilled off, 1- (n-butyl) -3,3-dimethyl-2 was obtained by vacuum distillation.
5.25 g of methylene-5,6-methylenedioxyindoline were obtained.

Boiling point 162-164 ° C./5 to 6 mmHg 1- (n-butyl) -3,3-dimethyl-2-methylene-5,6-methylenedioxyindoline obtained above
20 g into a mixture of 0 g and 100 ml of isopropyl alcohol.
Below 24 ° C. 3.24 g of 70% HClO ₄ were added. After stirring at room temperature for 1 hour, the mixture was cooled to 5 ° C or lower. The precipitated crystals are separated, washed and dried to give 1- (n-butyl) -2,3,3-trimethyl-
6.94 g of 5,6-methylenedioxyindolenium perchlorate was obtained.

 Melting point 147.0-150.0 ° C Preparation Example 1 Compound of general formula (2) [R¹= H, R^Two= N-butyl group,
X = O, Y = O, Z = ClO_Four 1.45 g, β-anilino
-0.52 g of acrolein-anil hydrochloride and potassium acetate
0.68 g was added to acetic anhydride 20 ml, and after refluxing for 10 minutes, water 100
ml. Separate the precipitated crystals, wash with water, and add methanol
Recrystallized from a compound of the general formula (1) [R¹= H, R^Two=
n-butyl group, X = O, Y = O, Z = ClO_Four , N =
2] 1.05 g was obtained. Melting point and maximum absorption wavelength of this compound
(Λmax) and molar extinction coefficient (ε) are as follows:
You.

 Melting point: 242.0-243.0 ° C λmax: 696 nm (methanol) ε: 1.76 × 10^Fivecm^-1 Production Example 2 Compound of general formula (2) [R¹= H, R^Two= Ethyl group, X =
O, Y = O, Z = I 9.34 g, β-anilino-ac
3.36 g of lorane-anil hydrochloride and 4.30 g of potassium acetate
Add 100 ml of acetic anhydride, reflux for 10 minutes, and then pour into 600 ml of water.
Entered. Separate the precipitated crystals, wash with water and re-use with methanol.
After crystallization, the compound of the general formula (1) [R¹= H, R^Two= Ethyl
Group, X = O, Y = O, Z = I , N = 2] 5.20 g
Was.

The maximum absorption wavelength (λmax) of this compound was 694 nm (methanol).

Production Example 3 Compound of general formula (2) [R¹= H, R^Two= 2-methoxye
Chill group, X = O, Y = O, Z = ClO_Four 9.41g, glue
3.74 g of taconaldehyde dianilide hydrochloride and potassium acetate
Was added to 100 ml of acetic anhydride and refluxed for 10 minutes.
Poured into 600 ml of water. Separate the precipitated crystals, wash with water,
After recrystallization from ethanol, the compound of the general formula (1) [R¹=
H, R^Two= 2-methoxyethyl group, X = O, Y = O, Z
= ClO_Four , N = 3] 6.00 g.

The maximum absorption wavelength (λmax) of this compound was 793 nm (methanol).

Production Example 4 Compound of General Formula (2) [R¹= Methyl group, R^Two= N-buty
Group, X = O, Y = methylene group, Z = ClO_Four 5.34g
And in the same manner as in Production Example 1, the compound of the general formula (1)
[R¹= Methyl group, R^Two= N-butyl group, X = O, Y = methyl
Len group, Z = ClO_Four , N = 2] 2.09 g. This transformation
Melting point of compound, maximum absorption wavelength (λmax) and molar extinction coefficient
(Ε) is as follows.

 Melting point: 227-228 ° C λmax: 695 nm (diacetone alcohol) ε: 1.94 × 10^Fivecm^-1 Production Example 5 Compound of general formula (2) [R¹= Methyl group, R^Two= N-buty
Group, X = methylene group, Y = O, Z = ClO_Four 5.34g
And in the same manner as in Production Example 1, the compound of the general formula (1)
[R¹= Methyl group, R^Two= N-butyl group, X = methylene group,
Y = O, Z = ClO_Four , N = 2] 2.76 g. This transformation
Melting point of compound, maximum absorption wavelength (λmax) and molar extinction coefficient
(Ε) is as follows.

 Melting point: 215-217 ° C λmax: 688 nm (diacetone alcohol) ε: 1.90 × 10^Fivecm^-1 Production Example 6 Compound of the general formula (2) [R¹= H, R^Two= N-butyl group,
X = methylene group, Y = methylene group, Z = ClO_Four 4.00
g and the compound of general formula (1) in the same manner as in Production Example 1.
Object (R¹= H, R^Two= N-butyl group, X = methylene group, Y =
Methylene group, Z = ClO_Four , N = 2] and 2.20 g were obtained.
The melting point, maximum absorption wavelength (λmax) and molar absorption of this compound
The optical coefficient (ε) is as follows.

 Melting point: 163-165 ° C λmax: 670 nm (diacetone alcohol) ε: 2.24 × 10^Fivecm^-1 Production Example 7 Compound of general formula (2) [R¹= H, R^Two= 2-ethoxy
Chill group, X = methylene group, Y = methylene group, Z = ClO_Four
In the same manner as in Production Example 1;
Compound (R¹= H, R^Two= 2-ethoxyethyl group, X = methyle
Group, Y = methylene group, Z = ClO_Four , N = 2]
Was. Maximum absorption wavelength (λmax) and molar absorption of this compound
The coefficient (ε) is as follows.

 λmax: 672nm (diacetone alcohol) ε: 2.20 × 10^Fivecm^-1 Production Example 8 Compound of General Formula (2) [R¹= H, R^Two= 2-acetoxy
Ethyl group, X = methylene group, Y = methylene group, Z = BF
_Four And the general formula (1)
Compound (R¹= H, R^Two= 2-acetoxyethyl group, X =
Tylene group, Y = methylene group, Z = BF_Four , N = 3]
Obtained. Maximum absorption wavelength (λmax) and molar absorption of this compound
The optical coefficient (ε) is as follows.

 λmax: 768nm ε: 2.28 × 10^Fivecm^-1 Production Example 9 Compound of the general formula (2) [R¹= H, R^Two= 2-methoxye
Chill group, X = methylene group, Y = methylene group, Z =
I And the general formula (1)
Compound (R¹= H, R^Two= 2-methoxyethyl group, X = methyl
Len group, Y = methylene group, Z = I , N = 3]
Was. Maximum absorption wavelength (λmax) and molar absorption of this compound
The coefficient (ε) is as follows.

λmax: 768 nm ε: 2.30 × 10 ⁵ cm ^-1 Production Example 10 Compound of the general formula (2) [R ¹ = H, R ² = 2-hydroxyethyl group, X = O, Y = O, And the compound of the general formula (1) [R ¹ = H, R ² = 2-hydroxyethyl group, X = O, Y =
O, n = 2]. Maximum absorption wavelength of this compound (λmax)
And the molar extinction coefficient (ε) are as follows.

 λmax: 695nm (diacetone alcohol) ε: 1.70 × 10^Fivecm^-1 Production Example 11 Compound of general formula (2) [R¹= H, R^Two= -C_TwoH_FourSO_ThreeNa
Group, X = O, Y = O, Z = Cl And the production example 1
Similarly, the compound of the general formula (1) [R¹= H, R^Two= -C_Two
H_FourSO_ThreeNa group, X = O, Y = O, Z = Cl , N = 3]
Obtained. Maximum absorption wavelength (λmax) and molar absorption of this compound
The optical coefficient (ε) is as follows.

 λmax: 790nm (methanol) ε: 1.60 × 10^Fivecm^-1 Production Example 12 Compound of general formula (2) [R¹= Methyl group, R^Two= N-buty
Group, X = O, Y = methylene group, Z = C_TwoH_FiveSO_Four ]
Using the compound of general formula (1) in the same manner as in Production Example 1
[R¹= Methyl group, R^Two= N-butyl group, X = O, Y = methyl
Len group, Z = C_TwoH_FiveSO_Four , N = 3]. This compound
Maximum absorption wavelength (λmax) and molar extinction coefficient (ε)
It is as follows.

λmax: 795 nm (methanol) ε: 1.93 × 10 ⁵ cm ^-1 <Reflectance measurement test> Various cyanine dyes shown in Table 1 below are dissolved in diacetone alcohol at a concentration of 30 g / ml, and this is put on an acrylic plate. Using a spin coater at 150 rpm, 600-700 in film thickness
ア ク リ ル was applied, dried, and the maximum reflectance from the substrate surface side of the acrylic plate at a wavelength of 770 nm to 800 nm was measured. The results are shown in Table 1.

<Solvent solubility> Various cyanine dyes shown in Table 2 below were dissolved in diacetone alcohol, and the solubility at room temperature was measured. The results are shown in Table 2.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification code FIG11B 7/24 516 B41M 5/26 Y (56) References International Publication 90/2735 (WO, A1) German Patent Publication 1923992 (DE) , A1) German Patent Publication 1805548 (DE, A1) (58) Fields investigated (Int. Cl. ⁶ , DB name) C09B 23/00 CA (STN)

Claims (1)

(57) [Claims] (1) General formula [In the formula, R ¹ represents a hydrogen atom or a lower alkyl group. R ² represents a lower alkyl group which may have a substituent. X and Y are the same or different and each represents a methylene group or an oxygen atom. Z represents an acidic residue. n represents 2 or 3. ] The cyanine type compound represented by these.